Anthraquinone dyes containing reactive groups



United States Patent 3,134,785 ANTHRAQUINONE DYES CONTAINING REACTIVE GROUPS Wolfgang Schoenaner and Francois Benguerel, Basel, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland No Drawing. Filed June 21, 1962, Ser. No. 204,081 Claims priority, application Switzerland June 22, 1961 4 Claims. (Cl. 260309.7)

This invention relates to dyes of the anthraquinone series containing at least one reactive group of the formula wherein halogen represents a halogen atom with an atomic Weight between 35 and 81, i.e. chlorine or bromine, and

, Y, represents an optionally halogenated alkylene or alkenylene radical.

A process for the production of these dyes comprises reacting anthraquinone dyes, which contain at least one aryl radical bound directly or through a bridge member, e.g. an oxygen atom, a sulfur atom or a group of the formula wherein R represents hydrogen or a substituted or unsubstitnted hydrocarbon radical, and containing at least one exchangeable hydrogen atom, with compounds of the formula in which A represents the radical of a dye of the anthraquinone series, which contains at least one aryl radical bound on the one hand directly with the methylene car- ,bon atom and on the other hand directly or through a bridge member with the anthraquinone nucleus, with a halogencarboxylic acid or with a functional derivative of a halogeno-carboxylic acid of the formula Halogen--YCOOH (IV) wherein Y has the aforecited meaning.

A series of particularly interesting dyes are those which 3,134,785 Patented May 26, 1964 correspond to the formula Z-n CH -CH O NH(arylene-CH;N N-O O-Y-ha1) H Hr1 CO fl-n H CHQHCHZ O NH-arylene-CH N N-C OY-ha1 wherein arylene is a phenylene radical which is preferably substituted by one to four alkyl groups with 1 to 4 carbon atoms,

R is a hydrogen orbromine atom, a methyl, methoxy or sulfonic acid group,

Y is a divalent saturated or unsaturated aliphatic radical which as up to 3 carbon atoms and may be halogenated,

hal represents a chlorine or bromine atom, and

n represents 1 or 2,

and the Whole molecule bears l to 2 sulfonic acid groups.

The anthraquinone dyes conforming to the invention are produced by reacting in acid medium anthraquinone compounds which contain at least one aryl radical bound directly or through a bridge member and containing at least one exchangeable hydrogen atom, with a compound of Formula II. The reaction is carried out advantageously in sulfuric or phosphoric acid of l0()% strength, preferably 100%, at temperatures of (]-40 C., preferably 5-20" C.

Of the compounds of Formula II the theoretical amount is sufiicient for the reaction, but it is advisable to use a slight excess. The resulting reaction products are worked up by precipitation from the sulfuric or phosphoric acid solution with water. Those dyestuffs conforming to the invention which contain water-solubilising groups are advantageously salted out from the aqueous acidic solution by the addition of salts such as sodium chloride.

Anthraquinone compounds with at least one aryl radical bound directly or through a bridge member and containing at least oneexchangeable hydrogen atom, which are particularly suitable for the production of the anthraquinone dyes conforming to the invention are:

1-amino-4-arylamino-anthraquinones, 1-amino-2-methyl-4-arylamino-anthraquinones, 1-amino-2-halogeno-4-arylamino-anthraquinones, l-amino-Z-alkoxy-4-arylamino-anthraquinones, 1-amino-2-aryloXy-4-hydroxy-anthraquinones, 1-amino-4-arylamino-anthraquinone-2-sulfonic acids, l,4-diamino-2-aryloxy-anthraquinones, 1-amino-4-arylamino-anthraquinone-2,5-(6,7 or 8)-disulfonic acids 1,4-diarylamino-anthraquinones 1,5-diamino-4,S-dihydroXy-Z-hydroxyphenyl-anthraquinones, 1,5-diamino-4,8-dihydroxy-Z-alkoxyphenyl-anthraquinones, 1,5-diamino-4,8-dihydroxy-Z-aryloxyphenyl-anthraquinones, 1,5-dihydroxy-4-amino-8-arylamino-anthraquinones, 1,5-dihydroxy-4-nitro-8-arylamino-anthraquinones.

.The compounds named may contain in the aryl nuclei, which are bound to anthraquinone directly or through a bridge member such as e.g. an oxygen atom, a sulfur atom or a group of the formula wherein R represents hydrogen or a substituted or unsub- 1.11 stituted hydrocarbon radical, further substituents such as alkyl, aryl, alkoxy, aryloxy, hydroxy, carboxy, cycloalkyl and aralkyl groups.

Suitable aryl radicals with at least one exchangeable hydrogen atom in the molecule are unsulfonated aryl radicals of the benzene, diphenyl or naphthalene series, for example the radicals: phenyl, 2-, 3- or 4-methyl-, -ethyl-, methoxy-or-ethoxyphenyl, 2,4-, 2,5- or 2,6-dimethyl-or -diethylphenyl, 2,4,6-trimethyl-or -triethylphenyl, 2,4,5-trimethylphenyl, 2,3,5,6- or 2,4,5,6-tetramethylphenyl, 2,3- or 3,4-tetramethylene-phenyl, 2,4- or 2,5-dimethoxyor-diethoxyphenyl, 2-chloro-4- or-6-methylphenyl, 2-methoxy-S-methylphenyl, 2-ethoxy-5-methylphenyl, 2- methoxy-4-methylphenyl, 2-methyl-4- or --methoxyor -ethoxyphenyl, 4-chloro-2,5-dimethoxyor -diethoxyphenyl, 4-chloro-2-methoxy-5-methy1phenyl, 2-chloro-4,6-dimethylphenyl, naphthyl-(1)-, naphthyl-(2), 2- or 4-methoxy-naphthyl-( 1 1,1'-diphenylyl-(4) Sulfonic acid groups can also be introduced into the anthraquinone compounds after the latter have been reacted with compounds of Formula II.

Suitable halogenocarboxylic acids of Formula IV and their functional derivatives which can be reacted with a compound of Formula III are the following: chloroacetic acid, bromoacetic acid, a-bromoand u-chloropropionic acid, fi-bromoand B-chloropropionic acid, abromoand fl-bromobutyric acid, oc-ChlOIO- and {it-chlorobutyric acid, a,,B-dibromopropionic acid, ogB-(liChlOIO- propionic acid, a-chloroand ot-bromoacrylic acid, 04,13- dichloroor a,{3-dibromoacrylic acid, 'y-chloroand 'ybromocrotonic acid etc. The --OC-Y-hal groups are also derived from these acids.

When the compounds (III) are water-soluble, the reaction of these with functional derivatives of halogenocarboxylic acids of Formula IV, e.g. with acid chlorides, is carried out preferably in aqueous medium at low temperatures e.g. between 0 and 30 C., and in presence of acid binding agents such as e.g. sodium or potassium acetate, bicarbonate, carbonate or hydroxide in finely pulverised form or in aqueous solutions, so that the reaction solution reacts weakly acid, neutral or Weakly alkaline. When the compounds (III) are not soluble in water, the reaction is carried out in aqueous suspension, aqueous organic or organic suspension or solution, the temperature of the reaction of compounds (III) being adjusted to the solvent used.

Providing they contain water-solubilizing groups the compounds produced which conform to the invention are extremely suitable for dyeing, padding and printing Wool and silk, natural and regenerated cellulose, and synthetic polyamide fibers, while those compounds which do not contain water-solubilizing groups, as disperse dyes give very good dyeing on linear polyesters, acetyl cellulose and in particular polyamides and basically modified polyacrylonitrile fibers. The dyeings obtained possess good light and wet fastness properties, in particular outstanding fastness to washing, water, sea water, perspiration and milling and also good fastness to rubbing, dry cleaning and organic solvents, provided they are linked to the fiber after application by a suitable aftertreatment e.g. in alkaline baths. They also have excellent fastness to sublimation, heat-setting and gas fumes.

In the following examples the parts and percentages are by weight and the temperatures in degrees Centigrade.

Example 1 9.5 parts of 1,4-di-(2',4,6'-trimethylphenylamino)- anthraquinone are dissolved with stirring at 15-20 in 140 parts of 96% sulfuric acid, 5.5 parts of N-chloroacetyl- N-hydroxymethyl-ethylene urea are added at -15 and the solution stirred at this temperature until no more 1,4 di-(2,4',6-trimethylphenylamino)-anthraquinone is indicated. After approprimately 4 hours the reaction is definitely completed. The solution is then poured onto 400 parts of ice. The resulting precipitate is filtered off, washed with water until of neutral reaction and dried. The dye obtained is reacted with 10-20% oleum for several hours at 20 to give a dyestulf which dyes wool in blue shades of good light and wet fastness and in particular good Washing and milling fastness. This dye contains per molecule approximately 1.5 reactive groups of the formula When in this process the amount of N-chloroacetyl- N-hydroxy-methyl-ethylene urea is increased to 9.5 parts, 2 reactive groups of Formula V per molecule are introduced.

A mercerised cotton fabric is printed with a printing paste of the following composition:

parts of the dye obtained by the procedure described above 100 parts of urea 397 parts of water 450 parts of 3 sodium alginate thickening 10 parts of sodium 3-nitrobenzene-sulfonate 20 parts of sodium carbonate 3 parts of sodium hydroxide solution 1000 parts The fabric is dried and steamed for 10 minutes at 102- 104, subsequently rinsed in cold and then in boiling water, soaped at the boil for 10 minutes with a 0.3% soap solution in distilled water, rinsed again in hot and cold water and dried.

A brilliant blue print is obtained which has excellent wet fastness properties.

Example 2 8.4 parts of 1,4-di-(4-methylphenylamino)-anthraquinone are dissolved with stirring at 15-20 in 140 parts of 96% sulfuric acid. 10 parts of N-chloroacetyl-N- hydroxymethyl-ethylene urea are added at 10-15 and the solution stirred at this temperature for 24 hours. The mass is then poured onto 400 parts of ice. The resulting precipitate is filtered off, washed with water until of new tral reaction and dried. On reaction with 20% oleum for several hours at 15 to 20 a dye is obtained Which dyes Wool in green shades fast to Washing and milling.

Example 3 11.6 parts of the sodium salt of l-amino-4-(2,4,6-trimethylphenylamino)-anthraquinone-Z-sulfonic acid are dissolved in 200 parts of 96% sulfuric acid at 5 to 10. 4.6 parts of N-chloroacetyl-N-hydroxymethyl-ethylene urea are added to this solution at 510 and the mass stirred for 4 hours at this temperature. The solution is then poured onto 250 parts of ice and 180 parts of saturated common salt solution. The resulting precipitate is filtered off and washed with a dilute common salt solution until of neutral reaction. The filter cake is suspended in Water and the pH adjusted to 7 by the addition of dilute sodium carbonate solution. The dye is then precipitated with common salt, filtered, washed with a dilute common salt solution and dried. It dyes Wool from weakly acid baths in blue shades. The dyeings are fast to washing and milling.

2 parts of the above dye, 0.8 part of an oxethylated fatty amine and 0.5 parts of an oleylpolyglycol ether are dissolved in 5000 parts of Water. 2 parts of glacial acetic acid are added to the bath which is then heated to parts of wool are entered and the bath brought to the boil in 30 minutes and maintained at this temperaturehfolr 45dnri1inu(;es.A'11he fabric is taken out of the bath, Formulae of representative dyes of the foregoing was e an rie eve dyeing, very fast to light and Wet treatments, is obtained. examples are asifouows.

When at the end of the dyeing process, the liquor is neutralised with 3 parts of 25% ammonia and the goods 5 treated for 20 minutes at 90, a dyeing is obtained which has somewhat better Wet fastness. The same effect can be obtained by treating the goods in a fresh bath con- Example 1 (second P p taimng 5000 parts of Water and 3 parts of hexamethylene tetramine for 20-30 minutes at 90-95. 1O 1 ('3Hz-CHa The follovymg table contams further reactive dyes of CH3 the anthraquinone series which are obtainable according 0 to the particulars of Examples 1 to 3. They correspond O NH 0 to the formula I] wherein the methylene group (CH 1s bound to an 0 NH CH aryl radlcal of A, and are characterized by the radlcal A, 20 I the aryl radical of A to which the methylene group is CH so H bound, the radical CO-Y-hal, the lnteger m and the shade of the dyemgs on wool 1n the columns (I) to (V).

(I) (II) (III) (IV) (V) Aryl radical to Which-011245 Shade of A=Radical of bound 0 0-Y-hal m the dyeing 011 wool l-amino-4-arylaminoanthraquinone- 2,4,6-trimethylpheny1 fll ropropionyL- 1 Blue.

2-suli0nic acid.

1 Do. 1 Do. 1 Do.

11. 2,6-dimethylphenyl 1 Do.

13- 2,5-dimethy1phenyl a-Chlorobutyryl.-. 1 Do.

14- 2,4,5,6-tetramethylpheny1 a-Ohloropropwnyl. 1 D

1 2,4,6rtriethy1phenyl Chloracetyl 1 D() 17- 4-methy1phenyl a,fl-Dibromopropiony 1 D 18. d0 a-Bromobutyryl 1 Do,

1 .-..do 4-ethy1phenyl 1 D 1-amjno-2-methy1-4-arylamino-anthra- 4-methy1-2(3)-suliopheny1 1 Do,

umone. f do 2,4,6-trimethyl-3-sulf0pheny1. 1 Do. do do v-Br0mocrotonyl H 1 Do. i-amino-2-bromo-4 arylamiuoanthra- 4-methyl-2-(3)-suli0pheny1 Chloroacetyl 1 Do.

umone.

24 "E 410 2,4,6-trimethyl3-su1fophenyl a-Bromoacrylyl 1 Do do 2,4,5trimethy1-3(6)-suliopheny1 fi-Oh1oropropionyL 1 Do. l-amino-2-methoxy-4-arylaminoan- 2,4-dimethyLK-suliophenyl. do 1 Do.

thraquinone.

do 2,4,B-trimethyl-Bsullophenyl. 1 Do. do 1 DO. 4-methy1-2(3)-sulfophenyl. 1 Do. 2,4-dimethy1-K-sulfophenyl 1 Do. do 2 Green. 2,6-dimethyl-K-sulfophenyL.- 2 Blue. dn a-Bromopropionyl 2 Do. 2,4,6-tr1methyL3-su1lophenyl 'y-Br0mocr0tonyL 2 D do a-Oh10robutyryl 2 D a,a Dichlor0pr0pi0ny1. 2 Do, do a-Chlor0acry1yl 2 Do. 4 methyl-2(3)-suliophenyl .....d0 2 Green. 4-isopropyl-2(3)-sulfopheny1 Ohloracetyl 2 Do. 2, 5-dimethyl-K-su1fophenyL do 2 Do. 2,4,o-triethyl-asulfophenyl- -do 2 Blue. 2,4-diethyl-K-sulfophenyi B-Ohloropropionyl 2 Green. 4-ethy1-2(3)-su1fophenyl a-(lhloraerylyLu 2 2,3,5,6tetramethylphenyl Ohloraeetyl 1 Blue.

2,4,5-trimethylphenyl do 1 Do. 2,4-dimethylphenyl Bromacetyl 1 Greenish ue. do a-ChlOlODIOIJiOHYl 1 Do.

2,4,6-trimethylpheny1 fl-Bromopropionyl 1 Blue. i do a,fl-D ichloroaerylyl. 1 Do. d 4-methy1pheny1 a-Bromoaerylylfi 1 Do. 51. -d0 4-ethy1phen Chioraeetyl 1 D 52 1-amino-4-ary1aminoanthraquinone-Z, 2,4,6-trimethylphenyl a-B-Dibromopropionyl 1 D0.

7-disu1f0nie acid.

4-methylpheny1 a-Bromopropionyl 1 Do, d0 Ohloracetyl 1 Do, do 2,4,6-trimethy1-3-bromophenyl do 1 Do do 1 Do. sulfonic acid.

(1 4-tert.butylpheny1.- 1 Do. 2,4,6-trimethyl-3-sulfophenyl. 1 Do, 4-methy1-2(3)-sulfophenyl 1 13 l-amino-4-arylamino-anthraquinone- Naphthyl-l- 1 Do.

2,7-disulf0nic acid. do Naphthy1'2- 1 Do.

56- l-amino-4-arylaminoanthraquinone-2- Example 2 (Harem CHl-N N-C -OH=01 so rr (|)H;CH, oHi-N N-O o-oIr, c1

O NH CH 50 E Example 3 CH,--CH,

on, oHP-N NC0--CH1C1 oo 0 NH-O-CHa Having thus disclosed the invention what we claim is: 1. An anthraquinone dye of the formula hal is a halogen atom with an atomic weight between 35 and 81, and

p is one of the integers 1 and 2, and SO H is present at least once and at most twice in the whole molecule.

2. The anthraquinone dye of the formula CH -OH om 0H,--N N-C O-CH -Cl C 0 NH -O H;

(3H3 SO3H CHg-CH CH3 CH2-N N-C OOH2C1 II C 0 0 NH -CHZ I OH: SOaH 3. The anthraquinone dye of the formula (111 -0 H, CH2 N\ /NC O-GHz-Cl O O E? I|\IH CII3 (Eng- C151 CH2-N\ /NC OCHzCI C 0 0 NlI- CH 4. The anthraquinone dye of the formula 0 NH, Ii 1 SO3H (|3H -C 0, on mi-Av N-C o-oH2o1 II C 0 0 NH- CH I OH;

References Cited in the file of this patent UNITED STATES PATENTS 2,226,909 Peter Dec. 31, 1940 2,245,780 Heinrich June 17, 1941 2,253,828 Von Allmen et al Aug. 26, 1941 OTHER REFERENCES Cheronis et al.: Semimicro Qualitative Organic Analysis, 2nd ed., page 3, N.Y., Interscience, 1947.

McElvain: The Characterization of Organic Compounds, revised edition, pp. 1-4, N.Y., MacMillan, 1953.

Shriner et al.: The Systematic Identification of Organic Compounds, 4th ed., page 1, N.Y., Wiley, 1956.

Skau et al.: Determination of Melting and Freezing Temperatures. In: Weissberger Physical Methods of Organic Chemistry, part 1, 3rd ed., page 288 (volume I- part I of Technique of Organic Chemistry), N.Y., Interscience, 1959.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 134,785 May 26, 1964 Wolfgang Schoenauer et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 18, for "as" read has column 7, lines 27 to 36, for the lower right-hand end of the formulav reading:

c11 co read fH CH N N-CO-Y-hal" N N COY-hal a co I co same column 7 lines 45 to 53, for that portion of the formula reading:

column 8 lines 30 to 38, for the right hand end of the formula reading;

-N N-CO-CHZCII N -co-cH -c1 co co Signed and sealed this 24th day of November 1964.

(SEAL) Attest ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. AN ANTHRAQUINONE DYE OF THE FORMULA 